Diastereo- and enantioselective chemical reactions have become essential for the efficient synthesis of complex chiral targets, including natural products, novel materials, biological probes, and pharmaceuticals. While the conventional approach toward asymmetric processes has relied upon intuitive or random screening approaches, the use of computational techniques to develop novel and improved methods has yet to be exploited. Our overall aim is to develop a series of rational design protocols for the identification of new chiral auxiliaries and catalysts for important synthetic reactions, that proceed through well delineated transition-states. In particular, we are using a process that identified noel ligand families via computational screening of data incorporated within large structural databases such as Cambridge Structural Database. As part of this program, we intend to demonstrate that high level ab initio calculations of transition state energies can be correlated to solution phase reactivity on a regular basis; such a result would provide an invaluable tool in reaction development. The success of this program could dramatically change the way chiral ligands are designed; even in a combinatorial setting, where novel core scaffolds could be selected that had a high probability of success upon optimization.